CN216669829U - Detection apparatus for synchronous acquisition three wave band electrochemiluminescence radiation intensity information - Google Patents

Detection apparatus for synchronous acquisition three wave band electrochemiluminescence radiation intensity information Download PDF

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CN216669829U
CN216669829U CN202220108684.7U CN202220108684U CN216669829U CN 216669829 U CN216669829 U CN 216669829U CN 202220108684 U CN202220108684 U CN 202220108684U CN 216669829 U CN216669829 U CN 216669829U
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ecl
dichroic mirror
radiation
electrochemical
pmt
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邹桂征
王东洋
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Shandong University
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Shandong University
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Abstract

The utility model relates to a detection device for synchronously acquiring electrochemical luminescence radiation intensity information of three wave bands, which comprises an electrochemical equipment unit, an ECL radiation generation unit, an ECL acquisition and photoelectric signal conversion unit and a computer, wherein the electrochemical equipment unit is connected with the computer; the ECL radiation generating unit comprises an ECL pool, a working electrode, a reference electrode and a counter electrode are arranged in the ECL radiation generating unit, and the ECL radiation collecting and signal converting unit comprises a collecting objective lens, a collimating lens, a first dichroic mirror, a second dichroic mirror and three PMTs; the electrochemical equipment unit is an integrated device comprising an electrochemical workstation module, a PMT high-voltage power supply module and a PMT signal acquisition module, and three PMT high-voltage power supply modules and three PMT signal acquisition modules are arranged in the electrochemical equipment unit. The utility model can accurately identify and synchronously acquire the intensity information of the ECL radiation of three wave bands, and can be used for wave band resolution type ECL single-component, double-component and three-component quantitative analysis.

Description

Detection apparatus for synchronous acquisition three wave band electrochemiluminescence radiation intensity information
Technical Field
The utility model relates to a detection device for synchronously acquiring electrochemiluminescence radiation intensity information of three wave bands, and belongs to the technical field of electrochemiluminescence detection devices.
Background
Electrochemiluminescence (ECL) is light radiation induced by an electrochemical redox reaction, and has the advantages of low background signal, wide linear range and high sensitivity. Conventional hardware devices for performing electrochemiluminescence analysis can be classified into two categories according to their source characteristics, namely: a commercialized electrochemical luminescence analyzer and an electrochemical luminescence detection device built by basic researchers. The conventional electrochemiluminescence detection device adopts a single photomultiplier structure which abandons a dispersion device, so that the electrochemiluminescence radiation can only be detected in total intensity, the electrochemiluminescence radiation of different wave bands cannot be identified on line, and the intensity information of the radiation of different wave bands cannot be recorded synchronously.
The inventor's earlier patent document CN205749297U discloses a detection system for collecting dual-wavelength electrochemiluminescence light intensity information, which adopts a mode of configuring a commercial photomultiplier tube (PMT) high-voltage power supply module device to supply power to two PMTs, uses an oscilloscope to synchronously collect output signals of the PMTs, and uses TTL signals to synchronously trigger an electrochemical device and a PMT output signal collection device, thereby realizing the synchronous collection of the electrochemiluminescence radiation intensity of two wave bands. Because the adoption of a single PMT power module to simultaneously supply power to a plurality of PMTs easily causes mutual perturbation among PMT output signals, the device is difficult to realize synchronous detection of the electrochemical luminescence radiation intensity of three wave bands in a simple PMT superposition mode.
Disclosure of Invention
Aiming at the defects of the prior art, especially the technical limitation that the prior art cannot synchronously acquire the intensity information of the electrochemiluminescence radiation of three wave bands and a single high-voltage power supply device supplies power to a plurality of PMTs simultaneously, the utility model provides the detection device for synchronously acquiring the ECL radiation intensity information of three wave bands.
The technical scheme of the utility model is as follows:
a detection device for synchronously acquiring ECL radiation intensity information of three wave bands comprises an electrochemical equipment unit, an ECL radiation generation unit, an ECL acquisition and photoelectric signal conversion unit and a computer, wherein the electrochemical equipment unit is connected with the computer;
the ECL radiation generating unit comprises an ECL cell, a working electrode, a reference electrode and a counter electrode are arranged in the ECL cell, and the working electrode, the reference electrode and the counter electrode are respectively connected with the electrochemical equipment unit;
the ECL radiation acquisition and signal conversion unit comprises a collection objective lens, a collimating lens, a first dichroic mirror, a second dichroic mirror and three PMTs; the light-emitting surface of the working electrode is over against the collecting objective lens, the collimating lens, the first dichroic mirror, the second dichroic mirror and the three PMTs are sequentially arranged along a light path, the transmission wavelengths of the first dichroic mirror and the second dichroic mirror are different, and the three PMTs are respectively connected with the electrochemical equipment unit through a signal line and a power line;
the electrochemical equipment unit is an integrated device comprising an electrochemical workstation module, a PMT high-voltage power supply module and a PMT signal acquisition module, and three PMT high-voltage power supply modules and three PMT signal acquisition modules are arranged in the electrochemical equipment unit.
According to the present invention, it is preferable that the first dichroic mirror is model number DMLP605L, and the second dichroic mirror is model number DMLP 730B. The dichroic mirror of the type has the advantages of obvious light splitting effect and high waveband resolution. The transmission wavelengths of the first dichroic mirror and the second dichroic mirror are different, so that the ECL radiation of three wave bands is ensured to be respectively collected by three PMTs, and the photoelectric signal conversion is synchronously carried out; the generated three paths of photovoltage signals are synchronously output to three PMT (photomultiplier tube) acquisition signal modules in the electrochemical equipment unit and are synchronously converted into digital signals, so that the synchronous detection of ECL (electron beam level) radiation intensity information of three wave bands is realized.
According to the utility model, preferably, the integrated device comprising the electrochemical workstation module, the photomultiplier tube power module and the signal acquisition module is a Senammy MPI-ME multi-channel electrochemical luminescence detector. The integrated device is internally provided with three PMT high-voltage power supply modules which can be synchronously started and respectively supply power for three PMTs, and the problem of signal perturbation caused by the fact that one high-voltage power supply device simultaneously supplies power for different PMTs in the existing device is solved. Meanwhile, the integrated device carries out miniaturization processing on the electrochemical workstation module, the PMT high-voltage power supply module and the PMT signal acquisition module, reduces the space and the number of the device and is convenient to carry and place.
According to the present invention, preferably, the bottom of the ECL cell is of a transparent structure, and further preferably, the ECL cell is of a fully transparent structure so as to facilitate the collection of all ECL information radiated by the working electrode by the collection objective lens. Preferably, the ECL cell is provided with an electrode fixing device, and the working electrode, the reference electrode and the counter electrode are all fixed on the electrode fixing device.
According to the present invention, preferably, the ECL radiation generating unit further includes an ECL cell holder having a light-transmitting hole at a bottom thereof, so that the ECL cell is fixed to the ECL cell holder. The light hole and the collimating lens are arranged oppositely along the light path, and the generated radiation is converted into parallel light to be vertically transmitted below the ECL cell.
According to the utility model, preferably, the detection device for synchronously acquiring the light intensity information of the ECL with three wave bands further comprises a dark box, wherein the ECL radiation generation unit, the collection objective lens, the collimator lens, the first dichroic mirror, the second dichroic mirror and the three PMT are arranged in the dark box;
preferably, the cassette is provided with a wire adapter, so that the connection between the electrodes and devices and the device outside the cassette is met on the premise of ensuring the complete closure of the light path;
preferably, a cassette switch door is further arranged at the top of the cassette;
preferably, the cassette is made of stainless steel, the inner surface of the cassette is coated with a corrosion-resistant material, and the outer surface of the cassette is coated with an insulating material. The cassette not only can effectively shield the interference of external electromagnetic radiation and stray light, but also can ensure that the whole system does not need a darkroom and is dustproof.
According to the utility model, preferably, the ECL radiation collection and signal conversion unit is further provided with an optical sleeve, and the collection objective lens, the collimating lens, the first dichroic mirror, the second dichroic mirror and the three PMTs are all arranged in the optical sleeve; preferably, the optical switch is arranged at the top end of the optical sleeve.
According to the present invention, it is preferable that the ECL cell is provided with an anti-reflection film to reduce radiation loss.
According to the present invention, it is preferable that the first dichroic mirror and the second dichroic mirror are each at an angle of 45 ° to the vertical direction. When ECL radiation light generated on the surface of the working electrode passes through the first dichroic mirror, radiation of a certain wave band penetrates through the dichroic mirror through transmission, and radiation of another wave band is converted into horizontal radiation through reflection and is collected by the first PMT; when the radiation passing through the first dichroic mirror passes through the second dichroic mirror, the radiation in a certain wave band is converted into the horizontal direction through reflection and is collected by the second PMT, and the radiation in another wave band passes through the dichroic mirror through transmission and is collected by the third PMT.
In the utility model, the light emitting surface of the working electrode is opposite to the collecting objective lens, the ECL radiation generated on the surface of the working electrode enters the ECL radiation collecting and signal converting unit after being collected by the collecting objective lens and is converted into parallel light by the collimating lens, and the light path connection of the ECL radiation generating unit and the ECL radiation collecting and signal converting unit is realized. Parallel light is split by the first dichroic mirror and the second dichroic mirror, then enters three different PMTs respectively, is synchronously converted into three paths of photovoltage signals, and the three paths of photovoltage signals are converted into three paths of digital signals by a PMT signal acquisition module in the electrochemical equipment unit and are synchronously input into a computer.
The principle of the utility model is as follows:
the method comprises the steps of loading a solution containing three substances with different ECL radiation wave bands and co-reactants thereof into an ECL cell, triggering a PMT high-voltage power supply module and a PMT signal acquisition module to synchronously operate when an electrochemical analyzer is started, generating ECL radiation with three wave bands on the surface of a working electrode, entering an ECL radiation acquisition and signal conversion unit through a collection objective lens, respectively entering three PMTs under the assistance of a first dichroic mirror and a second dichroic mirror, and synchronously converting three generated photoelectric voltage signals into digital signals by the three PMT signal acquisition modules arranged in an electrochemical equipment unit so as to realize synchronous, online and continuous acquisition of three-wave band ECL radiation intensity information under different electrochemical states. Dichroic mirrors with different specifications are selected to separate and synchronously collect different substances to generate ternary composite light.
The utility model has the following beneficial effects:
1. the utility model can accurately distinguish and synchronously collect the light intensity information of three-waveband ECL radiation, and is suitable for the quantitative analysis of waveband-distinguishing ECL single component, double component and three component.
2. The utility model overcomes the signal perturbation caused by the power supply device supplying power to different PMTs in the prior device.
3. The electrochemical equipment unit provided by the utility model has the advantages that the electrochemical workstation module, the PMT high-voltage power supply module and the PMT signal acquisition module are subjected to miniaturization processing, the electrochemical module, the PMT high-voltage power supply module and the PMT signal acquisition module are started by adopting unified software, TTL (transistor-transistor logic) triggering is not required, and the electrochemical equipment unit is convenient to carry and place.
Drawings
FIG. 1 is a schematic diagram of a main structure of a detection device for synchronously acquiring electrochemiluminescence radiation intensity information of three bands according to the present invention.
1. An electrochemical and photomultiplier power supply integrated module, 2, an ECL cell, 3, an electrode fixing device, 4, a reference electrode, 5, a counter electrode, 6, a working electrode, 7, an ECL cell support, 8, a cassette, 9, a cassette switch door, 10, an optical switch, 11, a collection objective lens, 12, a collimating mirror, 13, an optical sleeve, 14, a first dichroic mirror, 15, a second dichroic mirror, 16, PMT, 17, a lead switching port, 18, a signal wire, 19, a power wire, 20 and a computer.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
In the embodiment, the first dichroic mirror 14 is of the model number DMLP605L, and the second dichroic mirror 15 is of the model number DMLP 730B. The dichroic mirror of the type has the advantages of obvious light splitting effect and high waveband discrimination.
The electrochemical analyzer used in the examples is a Sienna Ruima MPI-ME multi-channel electrochemical luminescence detector.
Example 1
As shown in fig. 1, a detection apparatus for synchronously acquiring electrochemiluminescence radiation intensity information of three wave bands comprises an electrochemical device unit, an ECL radiation generation unit, an ECL radiation acquisition and signal conversion unit, and a computer, wherein the electrochemical device unit is connected with the computer;
the ECL radiation generating unit comprises an ECL cell 2, a working electrode 6, a reference electrode 4 and a counter electrode 5 are arranged in the ECL cell 2, and the working electrode 6, the reference electrode 4 and the counter electrode 5 are respectively connected with an electrochemical equipment unit;
the ECL radiation acquisition and signal conversion unit comprises a collection objective lens 11, a collimating mirror 12, a first dichroic mirror 14, a second dichroic mirror 15 and three PMT 16; the light-emitting surface of the working electrode 6 is opposite to the collecting objective lens 11, the collimator lens 12, the first dichroic mirror 14, the second dichroic mirror 15 and the three PMT16 are sequentially arranged along a light path, the transmission wavelengths of the first dichroic mirror 14 and the second dichroic mirror 15 are different, and the three PMT16 are respectively connected with the electrochemical equipment unit through a signal line 18 and a power line 19;
the electrochemical equipment unit is an integrated device 1 comprising an electrochemical workstation module, a PMT high-voltage power supply module and a PMT signal acquisition device, and the integrated device 1 is internally provided with three electrochemical workstation modules, three PMT high-voltage power supply modules and three PMT signal acquisition modules.
The integrated device 1 (namely, the electrochemical equipment unit) is a Siemens-Meyer MPI-ME multi-channel electrochemical luminescence detector. The three PMT high-voltage power supply modules arranged in the electrochemical equipment unit can supply power for the three PMTs, and the problem of signal interference caused by the fact that one high-voltage power supply device supplies power for different PMTs simultaneously in the existing device is solved. Meanwhile, the electrochemical equipment unit carries out miniaturization processing on the electrochemical workstation module, the PMT high-voltage power supply module and the PMT signal acquisition module, reduces the space and the number of the device and is convenient to carry and place.
First dichroic mirror 14 and second dichroic mirror 15 each make an angle of 45 ° with the vertical direction. After ECL radiation light generated on the surface of the working electrode 6 passes through the first dichroic mirror 14, radiation of a certain waveband is completely transmitted, and radiation of the other part of waveband is converted from the vertical direction to the horizontal direction through reflection and then is transmitted into one PMT; when the radiation transmitted through the first dichroic mirror passes through the second dichroic mirror 15, the radiation of a certain wavelength band is converted from the vertical direction into the horizontal direction through reflection and then is transmitted into the second PMT; another band of radiation is transmitted completely into the third PMT.
Example 2
As described in example 1, except that:
the ECL cell 2 is of a full transparent structure so that the ECL information radiated by the working electrode 6 is collected by the collecting objective lens 11. The ECL cell 2 is provided with an electrode fixing device 3, and the working electrode 6, the reference electrode 4 and the counter electrode 5 are all fixed on the electrode fixing device 3.
Example 3
As described in example 1, except that:
the ECL radiation generating unit further comprises an ECL cell bracket 7 with a light hole at the bottom, so that the ECL cell 2 is fixed on the ECL cell bracket 7. The light hole is arranged opposite to the collimating mirror 12 along the light path, and the generated radiation is converted into parallel light and is vertically transmitted to the lower part of the ECL cell 2.
Example 4
As described in example 1, except that:
the detection device for synchronously acquiring the intensity information of the electrochemiluminescence radiation of the three wave bands further comprises a cassette 8, wherein the ECL radiation generation unit, the collection objective lens 11, the collimator lens 12, the first dichroic mirror 14, the second dichroic mirror 15 and the three PMT16 are arranged in the cassette 8;
the cassette 8 is provided with a wire adapter 17, so that the connection between electrodes and devices and a device outside the cassette 8 is met on the premise of ensuring the complete closure of a light path;
the top of the cassette 8 is also provided with a cassette switch door 9;
the cassette 8 is made of stainless steel, the inner surface of the cassette 8 is coated with corrosion-resistant material, and the outer surface of the cassette 8 is coated with insulating material. The cassette 8 can effectively shield the interference of external electromagnetic radiation and stray light, and can ensure that the whole system does not need a darkroom and is dustproof.
Example 5
As described in example 1, except that:
the ECL radiation collection and signal conversion unit is also provided with an optical sleeve 13, and the collection objective lens 11, the collimating lens 12, the first dichroic mirror 14, the second dichroic mirror 15 and the three PMT16 are all arranged in the optical sleeve 13; the optical switch 10 is arranged at the top end of the optical sleeve 13.

Claims (9)

1. A detection device for synchronously acquiring electrochemiluminescence radiation intensity information of three wave bands comprises an electrochemical equipment unit, an ECL radiation generation unit, an ECL acquisition and photoelectric signal conversion unit and a computer, wherein the electrochemical equipment unit is connected with the computer;
the ECL radiation generating unit comprises an ECL cell, wherein a working electrode, a reference electrode and a counter electrode are arranged in the ECL cell, and the working electrode, the reference electrode and the counter electrode are respectively connected with an electrochemical equipment unit;
it is characterized in that the preparation method is characterized in that,
the ECL radiation acquisition and signal conversion unit comprises a collection objective lens, a collimating lens, a first dichroic mirror, a second dichroic mirror and three PMTs; the light-emitting surface of the working electrode is over against the collecting objective lens, the collimating lens, the first dichroic mirror, the second dichroic mirror and the three PMTs are sequentially arranged along a light path, the transmission wavelengths of the first dichroic mirror and the second dichroic mirror are different, and the three PMTs are respectively connected with the electrochemical equipment unit through a signal line and a power line;
the electrochemical equipment unit is an integrated device comprising an electrochemical workstation module, a PMT high-voltage power supply module and a PMT signal acquisition module, and three PMT high-voltage power supply modules and three PMT signal acquisition modules are arranged in the electrochemical equipment unit.
2. The apparatus according to claim 1, wherein the first dichroic mirror is DMLP605L, and the second dichroic mirror is DMLP 730B.
3. The detecting device for synchronously acquiring the information on the radiation intensity of electrochemiluminescence with three wavebands according to claim 1, wherein the electrochemical equipment unit is a SeamRaima MPI-ME multi-channel electrochemiluminescence detector.
4. The apparatus according to claim 1, wherein the bottom of the ECL cell is transparent, the ECL cell is provided with an electrode fixing device, and the working electrode, the reference electrode and the counter electrode are fixed on the electrode fixing device.
5. The device of claim 1, wherein the ECL radiation generating unit further comprises an ECL cell holder having a light hole at the bottom.
6. The apparatus according to claim 1, wherein the apparatus further comprises a dark box, and the ECL radiation generating unit, the collecting objective, the collimator, the first dichroic mirror, the second dichroic mirror, and the three PMTs are disposed in the dark box.
7. The apparatus as claimed in claim 6, wherein the cassette is provided with a wire adapter, and a cassette door is further provided on the top of the cassette.
8. The device of claim 1, wherein the ECL radiation collection and signal conversion unit further comprises an optical sleeve, and the collection objective, the collimator, the first dichroic mirror, the second dichroic mirror, and the three PMTs are disposed in the optical sleeve.
9. The device of claim 1, wherein the first dichroic mirror and the second dichroic mirror are both at an angle of 45 ° to vertical.
CN202220108684.7U 2022-01-17 2022-01-17 Detection apparatus for synchronous acquisition three wave band electrochemiluminescence radiation intensity information Active CN216669829U (en)

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